A 1,4-benzodioxane derivative is used for an intermediate for preparation of circulatory drugs and drugs for psychoneurosis which are .alpha.- and .beta.-adrenergic antagonist-activity and its various kind of processes are known. For example, the method by reacting a catechol derivative with glycidyl tosylate in the presence of sodium hydride (Japanese patent publication No.6-9613(1994)) or the method by reacting a catechol derivative with epichlorohydrin in the presence of pyridine (J. Org. Chem. 46,3846(1981)) is known. A method is also known to make a 1,4-benzodioxane skeleton by reacting a catechol derivative with glycerol 1-tosylate acetonide and, after removing the protective group, the acetonide, by introducing two tosyl group onto it and then by isolating it, and further by cyclizing it (J. Chem. Soc., Chem. Commun., 921(1976)).